Apparatus and methods for parallel processing of multiple reaction mixtures

ABSTRACT

A parallel reactor system including a reactor and vessels in the reactor for holding reaction mixtures, and a cannula for introducing fluid reaction material into the vessels. A robot system is operable to insert the cannula into cannula passages in the reactor for delivery of reaction materials, including slurries, to respective vessels, and to withdraw the cannula from the cannula passages after delivery. Related methods are also disclosed.

BACKGROUND OF THE INVENTION

[0001] The present invention relates generally to parallel reactors, andin particular, to parallel research reactors suitable for use in acombinatorial (i.e., high-throughput) science research program in whichchemical reactions are conducted simultaneously using small volumes ofreaction materials to efficiently and economically screen largelibraries of chemical materials.

[0002] The present invention is related to co-owned InternationalApplication No. PCT/US 99/18358, filed Aug. 12, 1999 by Turner et al.,entitled Parallel Reactor with Internal Sensing and Method of UsingSame, published Feb. 24, 2000 (International Publication No. WO00/09255), and which is incorporated herein by reference for allpurposes. This PCT application claims priority from the followingco-owned, co-pending U.S. applications bearing the same title, all ofwhich are also incorporated by reference: Ser. No. 09/211,982, filedDec. 14, 1998 by Turner et al. and Ser. No. 09/177,170, filed Oct. 22,1998 by Dales et al., claiming the benefit of provisional applicationSer. No. 60/096,603, filed Aug. 13, 1998 by Dales et al. The presentinvention is also related to co-owned, co-pending U.S. application Ser.No. 09/548,848, filed Apr. 13, 2000 by Turner et al., entitled ParallelReactor with Internal Sensing and Method of Using Same, claimingpriority from the aforementioned PCT application; U.S. application Ser.No. 09/239,223, filed Jan. 29, 1999 by Wang et al., entitled Analysisand Control of Parallel Chemical Reactions; U.S. application Ser. No.60/209,142, filed Jun. 2, 2000, by Nielsen et al., entitled ParallelSemicontinuous or Continuous Stirred Reactors; and U.S. application Ser.No. 60/255,716, filed Dec. 14, 2000, by Nielsen et al., entitledParallel Semicontinuous Stirred Reactors, all of which are herebyincorporated by reference for all purposes. These applications disclosea number of embodiments for parallel research reactors suitable for use,for example, in combinatorial chemistry applications such as polymerresearch and catalyst research. However, these embodiments are notespecially suited for processing certain slurry materials, such as thosecontaining small particle solids (e.g., silica or alumina particles usedas catalyst supports) which can cause excessive wear and/or impedeproper operation of reactor equipment, or slurries having aggressivebonding characteristics, which may make them difficult to handle and toclean from reactor equipment. There is a need, therefore, for a systemcapable of handling such materials.

SUMMARY OF THE INVENTION

[0003] In view of the foregoing, the objectives of this inventioninclude the provision of a parallel reactor and related methods whichovercome deficiencies of known parallel reactors, especially parallelresearch reactors and methods; the provision of such a parallel reactorand methods which allow for the efficient handling of slurry reactantmaterials, including slurries containing small particles of solidmaterial, such as silica, and slurries which are especially “sticky” andthus difficult to handle; the provision of such a reactor and methodswhich provide for the delivery of precise quantities of reactantproducts, including slurries, to the reaction vessels of a parallelreactor; and the provision of such a reactor and methods which providefor the delivery of slurry and other reaction materials under pressureand/or temperature to one or more reaction chambers of the reactor.

[0004] In general, apparatus of the present invention is operable forprocessing multiple reaction mixtures in parallel. In one aspect, theapparatus comprises a reactor having an exterior surface, and vessels inthe reactor for holding the reaction mixtures, each vessel having acentral longitudinal axis. A cannula is used for introducing fluidreaction material into the vessels. The cannula has a longitudinal axis,a distal end, and a port generally adjacent said distal end for deliveryof reaction material from the cannula. Cannula passages in the reactorextend between the exterior surface of the reactor and the vessels. Eachpassage extends at an angle relative to the central longitudinal axis ofa respective vessel. A robot system is operable to insert the cannulathrough a selected cannula passage and into a respective vessel for thedelivery of the reaction material from the cannula to the respectivevessel, and to withdraw the cannula from the selected cannula passageand respective vessel.

[0005] Another aspect of the present invention involves a method ofloading fluid reaction material into a series of vessels in a reactor,each vessel having a central longitudinal axis. The method comprises, insequence, (1) inserting a cannula through a cannula passage in thereactor to a position in which the cannula extends at an angle relativeto the central longitudinal axis of a first vessel of the series ofvessels, and in which a distal end of the cannula is disposed in thevessel, (2) delivering a fluid reaction material from the cannula intothe vessel, (3) withdrawing the cannula from said passage, and repeating1-3 for a second vessel.

[0006] The present invention is also directed to a cannula for use inaspirating reactant materials and delivering such materials to reactionvessels for the parallel processing of such materials. The cannulacomprises a tubular metal reservoir having a longitudinal axis, aninside diameter defining a hollow interior for containing said reactantmaterials, an outside diameter, a proximal end and a distal end. Thecannula also includes a long straight thin needle formed from metaltubing and coaxial with the reservoir. The needle has an outsidediameter substantially less than the outside diameter of the reservoirand an inside diameter defining a flow passage through the needle. Theneedle further has a proximal end, a distal end, and a port adjacent thedistal end for aspirating reactant materials into the needle anddelivering reactant materials from the needle. A metal transition joinsthe proximal end of the needle to the distal end of the reservoir sothat the hollow of the interior of the reservoir is in fluidcommunication with the flow passage of the needle.

[0007] Another aspect of the present invention involves vessels designedfor placement in a series of vertical cylindric wells in a parallelreactor of the type having cannula passages extending at an angle offvertical from an exterior surface of the reactor to the wells, eachcannula passage being adapted for the passage therethrough of a cannulacontaining reaction material to be delivered to a respective vessel.Each vessel has a bottom and a cylindric side wall extending up from thebottom and terminating in a rim defining an open upper end of thevessel. The cylindric side wall has an inside diameter in the range of0.5-2.5 in. The vessel has a volume in the range of 5-200 ml. and anoverall height in the range of 1.0-4.0 in., such that when the vessel isplaced in a well of the reactor, the open upper end of the vessel isdisposed at an elevation below the cannula passage where the cannulapassage enters the well and is positioned for entry of the cannula downthrough the open upper end of the vessel to a position below the rim ofthe vessel for the delivery of reactant materials into the vessel.

[0008] In yet another aspect, the present invention involves a method ofpreparing and delivering a slurry reaction material into a series ofvessels in a reactor. The method comprises (1) mixing a particulatesolid material and a liquid to form a substantially homogeneous firstslurry in which the particulate solid material is suspended in theliquid, (2) aspirating the first slurry into a cannula carried by arobot system while the slurry is substantially homogeneous, (3)operating the robot system to insert the cannula into the reactor, (4)delivering the slurry from the cannula into the vessel while the cannulais in said cannula passage, and (5) repeating 2-4 for a second vesseland optionally a second slurry.

[0009] Other objects and features will be in part apparent and in partpointed out hereinafter.

BRIEF DESCRIPTION OF THE DRAWINGS

[0010]FIG. 1 is a perspective of a parallel reactor of the presentinvention;

[0011]FIG. 2 is a schematic diagram showing key components of thereactor for delivering a slurry fluid to a number of reactor modules;

[0012]FIG. 3 is an enlarged portion of FIG. 1 showing, among otherthings, a modular reactor and a robot system for servicing the reactor;

[0013]FIG. 4 is an enlarged portion of FIG. 3 showing a shaker and hotand ambient wash towers;

[0014]FIG. 5 is an enlarged portion of FIG. 3 showing several reactormodules mounted on a series of interconnected carriage plates:

[0015]FIG. 6 is a perspective of a heated wash tower of the presentinvention;

[0016]FIG. 7 is a top view of the heated wash tower;

[0017]FIG. 8 is a vertical section on lines 8-8 of FIG. 7;

[0018]FIG. 9 is a top view of a reactor module showing a cannulaimmediately prior to the delivery of fluid to a vessel in the module;

[0019]FIG. 10 is a vertical section along lines 10-10 of FIG. 9 showingthe construction of a reactor module and cannula for delivering fluid(e.g., in slurry form) to a vessel in the reactor module;

[0020]FIG. 11 is a vertical section on line 11-11 of FIG. 9 in a planethrough the central axis of the vessel;

[0021] FIGS. 12-14 are sequential views illustrating various steps inthe procedure for delivering fluid to a vessel via the cannula;

[0022]FIG. 15 is a perspective of key components of the robot system,showing the cannula in a travel position with the head of the support ina lowered position down on the needle of the cannula;

[0023]FIG. 16 is a view similar to FIG. 15 showing the cannula in afluid delivery position, with the head of the support in a raisedposition up on the needle;

[0024]FIG. 17 is a perspective showing a mechanism for rotating theright robot arm about its axis, the mechanism being shown in a flat ornon-rotated position;

[0025]FIG. 18 is a view similar to FIG. 17 showing the mechanism in arotated position;

[0026]FIG. 19 is a view similar to FIG. 18 but showing the mechanism asviewed from an opposite end of the mechanism;

[0027]FIG. 20 is a perspective showing a mechanism for rotating the leftrobot arm about its axis, the mechanism being shown in a flat ornon-rotated position;

[0028]FIG. 21 is a view similar to FIG. 20 showing the mechanism in arotated position;

[0029]FIG. 22 is a view similar to FIG. 20 but showing the mechanism asviewed from below;

[0030]FIG. 23 is a side elevation of the cannula, with part of thecannula being shown in section to illustrate details;

[0031]FIG. 23A is an enlarged view showing details of the constructionof the cannula of FIG. 23;

[0032]FIG. 24 is an enlarged view of a port of the cannula;

[0033]FIG. 25 is a section taken on line 25-25 of FIG. 24;

[0034]FIG. 26 is a front elevation of a mount for mounting the cannulaon the robot system, and a support for supporting a needle of thecannula;

[0035]FIG. 27 is a vertical section taken on lines 27-27 of FIG. 26; and

[0036]FIG. 28 is an enlarged portion of FIG. 27 showing a head of thesupport.

[0037] Corresponding parts are designated by corresponding referencesnumbers throughout the drawings.

DESCRIPTION OF PREFERRED EMBODIMENTS

[0038] Referring now to the drawings, and more particularly to FIG. 1,apparatus for parallel processing of multiple reaction mixtures isindicated in its entirety by the reference numeral 1. (As used herein,the term “parallel” means that two or more of the multiple reactionmixtures are processed either simultaneously or at least duringoverlapping time periods.) The apparatus 1, which may be referred to asa parallel reactor system, is similar in certain respects to theparallel reactor system described in the aforementioned publications andapplications, including U.S. application Ser. No. 09/548,848.

[0039] In general, the apparatus 1 comprises an enclosure 3 having afloor 4, a rail system generally designated 5 on the floor 4, and acarriage generally designated 7 slidable on the rail system. A modularreactor 9 comprising a number of reactor modules, each generallydesignated 9M, are mounted side-by-side on the carriage. Six suchreactor modules 9M are shown in FIGS. 1-3, but this number may vary fromone to six or more. Further, the reactor need not be modular, but ratherit could be a single monolithic reactor. The reactor 9 is preferably aresearch reactor, but could also be a relatively small-volume productionreactor. Two orbital shakers 13 are provided on the carriage 7 forshaking fluid reactants or other reaction materials in mixing vials 15held by racks 17 mounted on the shakers (FIG. 4). The reaction materialsmay be in slurry form comprising solid particles, such as silica oralumina particles supporting a catalyst, suspended in a carrier fluid.The apparatus 1 further includes a pair of cannulas, each generallydesignated 21, and a four-axis robot system, generally indicated at 23,for moving the cannulas to aspirate fluid reaction materials from thevials into the cannulas, and then to move the cannulas into position fordelivery of the fluid materials to the reactor modules 9M, as will bedescribed. Alternatively, a single cannula or more than two cannulascould be used to service the reactor modules. Apparatus, generallydesignated 25, for cleaning the cannulas is also provided on thecarriage adjacent each orbital shaker.

[0040] In the preferred embodiment, the robot system 23, carriage 7,rail system 5 and various components on the carriage are all enclosed bythe enclosure 3, which is a tubular enclosure supported by legs. (Forconvenience of illustrating the equipment inside the enclosure, certainportions of the top and side walls of the enclosure are omitted in FIG.1.) The enclosure is preferably what is referred to as a “dry box” or a“glove box” having gloves 33 affixed to the periphery of openings 35 inthe side walls of the enclosure to allow an operator to manipulate itemsinside the enclosure and reduce possible contamination. The enclosure 3can be gas-tight or filled with a pressurized inert gas (e.g., argon ornitrogen). In either case, the environment is controlled to eliminatecontaminants or other material which might interfere with the parallelreaction processes being conducted in the enclosure. Conventionalantechambers (air locks) 37 on the enclosure provide access to theinterior of the enclosure. Glove box enclosures suitable for use in thepresent invention are available from, among others, Vacuum AtmospheresCompany of Hawthorne, Calif., and M. Braun Inc. of Newburyport, Mass.Other types of enclosures may also be used, such as a purge box which ismovable between a non-enclosing position and an enclosing position andpurged of contaminants with a pressurized inert gas.

[0041] Also disposed within the enclosure 3 is suitable pumpingequipment 41 for servicing the two cannulas 21, as schematically shownin FIG. 2. This equipment is of conventional design and may comprise,for example, positive displacement pumps, preferably adapted for smallvolume increments. Exemplary pumps include four syringe pumps 43 in ahousing 45, each syringe pump comprising a pump and associated syringe.In this embodiment, one set of two syringe pumps 43 services one cannula21 and the other set of two syringe pumps 43 services the other cannula21. Preferably, one syringe pump 43 a of each two-pump set is operableto pump a larger (but still relatively small) volume of fluid, e.g., 5ml to 25 ml, and the other syringe pump 43 b of the two-pump set isoperable to pump a smaller volume, e.g., 100 μl to 1 ml. The amount offluid pumped for any given reaction preferably will vary from about 5 μlto about 500 ml, more preferably from about 1 ml to about 500 ml, stillmore preferably from about 1 ml to about 100 ml, yet more preferablyfrom about 2 ml to about 50 ml, still more preferably from about 2 ml toabout 25 ml, and most preferably from about 5 ml to about 15 ml. The twopumps of each two-pump set are connected to a supply 49 of working fluid(e.g., solvent) by a flow line 51. The construction and operation of thesyringe pumps 43 is conventional, such pumps being commerciallyavailable from Cavro Scientific Instruments of Sunnyvale, Calif., pumppart No. 730367 and syringe part No. 730320. Accordingly, a detaileddescription of these syringe pumps is unnecessary. Suffice it to saythat they are operable in two modes, the first being an intake mode toaspirate measured quantities of fluid reaction material into thecannulas 21, and the second being an output mode to pump measuredvolumes of working fluid to the cannulas 21 to force correspondingvolumes of reaction material from the cannulas for delivery to thereactors 9M. Generally speaking, the smaller volume syringe pump 43 b isused to pump smaller volumes of fluid, and the larger volume syringepump 43 a is used to pump larger volumes of process material. In theevent fluid must be supplied under pressure to a reactor module 9M, thesmaller volume syringe pump 43 b is preferably used, since it isoperable to supply fluids at pressures up to 500 psig. or more.

[0042] The enclosure 3 is provided with fittings 55 for attachment oflines 57 which service the reactor modules. These lines 57 are typicallyused for the delivery of process gases (e.g., reactant and quenchinggases) to the reactor modules 9M, as needed, and also to vent themodules, as will be described hereinafter. The gas lines 57 communicatewith suitable sources of gas (not shown) under pressure. The pressure ofthe gas in the lines 57 is controlled by regulators indicated at 59 inFIG. 1.

[0043] Referring to FIG. 3, the rail system 5 comprises a pair of guiderails 61 (e.g., linear guide rails of the type available from ThomsonIndustries, Port Washington, N.Y.) mounted on the table. Slide bushings63 mounted on the underside of the carriage allow the carriage 7 toslide back and forth on the rails.

[0044] The carriage 7 itself (FIGS. 3 and 5) comprises a plurality ofinterconnected carriage plates 67, including two end plates 67 acarrying the orbital shakers 13, cleaning apparatus 25 and othercomponents, and a plurality of intermediate plates 67 b, each of whichcarries a single reactor module 9M. Adjacent carriage plates 67 areconnected by rabbet joints 71 comprising overlapping recessed edgemargins releasably secured in precise position relative to one anotherby quick-connect/disconnect devices 75, each of which extends downthrough aligned holes in the plates. The device may comprise, forexample, a vertical shaft 77 having one or more detents (not shown) atits lower end spring-biased to an extended position for reception incorresponding recesses in the lower of the two overlapping edge margins(see FIG. 5), and a manually-operated button 79 at the upper end of theshaft for retracting the detents to allow the shaft to be withdrawn fromthe holes to disconnect the two carriage plates 67. Upon disconnection,the carriage plates 67 can be moved together as a unit or relative toone another on the rails 61 to facilitate maintenance and repair of theequipment on the carriage as well as to vary the number of carriageplates and reactor modules in the reactor matrix. The carriage 7 is heldin a fixed, predetermined home position on the floor 4 by a “master”interlock 81 (similar to the quick connect/disconnect devices)connecting a rigid extension 83 projecting from the carriage to astationary fixture 85 affixed to the floor (FIG. 3). In the preferredembodiment, disconnection of the “master” interlock 81 to disconnect thecarriage 7 from the fixture 85 triggers a shut-off switch which preventsoperation of the robot system 23 until the interlock is reinstalled toreconnect the carriage extension 83 to the fixture 85 at the homeposition. Such reconnection requires precise alignment of holes in theextension and the fixture, which in turn requires that all carriageplates 67 be properly connected and positioned relative to one another.Thus, the robot system 23 cannot be operated until the carriage plates67 (and all of the components fixedly attached thereon) are preciselylocated on the floor 4.

[0045] As shown in FIG. 4, each vial rack 17 is releasably held in aframe 91 mounted in fixed position on its respective shaker 13. Springclamps, quick-acting detents 93 or other connectors on the frame 91 maybe used for this purpose. The fit between the rack 17 and the frame 91is a relatively close, tight fit so that the position of each vial inthe rack is set for purposes of the computer controlled robot system 23.The rack 17 itself is modular in design, comprising a plurality ofhorizontal panels 95 held in vertically spaced relation by spacers 97fastened to the panels. The panels have vertically aligned openings 99therein for receiving and holding the vials. The modular nature of theconstruction facilitates different rack configurations, all of which canfit in the same frame 91. For example, the configuration of the rack canbe readily changed to accommodate vials of different sizes, or differentnumbers of vials, or vials arranged in different arrays. Also, the useof relatively thin panels 95 (which may be stamped metal parts) andspacers reduces the weight of the assembly.

[0046] Referring again to FIG. 4, the cleaning apparatus 25 comprises aconventional wash tower 101 having a cavity or well 103 therein forreceiving a cannula 21 to be washed and rinsed. Suitable cleaningsolution (e.g., solvent) at ambient temperature is pumped through thecannula to flush its interior surfaces. Solution exiting the cannula 21is directed by the walls of the cavity up along the outside of thecannula to clean its exterior surfaces. Waste solution is directed to adrain 107 for disposal (FIG. 2). A wash tower 101 suitable for use inthe system is available from Cavro Scientific Instruments of Sunnyvale,Calif., Model No. 727545.

[0047] In the event there is a need for more aggressive washing of acannula, as when slurry reaction materials containing small particulatesolids (e.g., solution phase supported catalysts) that tend to adhere toprocess equipment are being used, the cleaning apparatus 25 may includean ultrasonic bath (not shown) and/or a separate heated wash towergenerally indicated at 111. The construction of the heated wash tower isillustrated in FIGS. 6-8. As shown, the tower 111 comprises an uprightgenerally channel-shaped housing 113 on a base 115 secured to an endcarriage plate 67 a, and a cylindric block 117 of metal supported withinthe housing having a flanged and recessed upper end 119 and two bores121, 123 extending down into the block 117 from the recessed upper end119. The first bore 121 forms a washing well and is relatively narrow indiameter, being only slightly larger in diameter (e.g., 0.035 in.larger) than the outside diameter of the needle of a cannula 21 to bewashed. The second bore 123 is larger in diameter and functions as adrain. Intersecting countersinks 121 a, 123 a at the upper ends of thetwo bores 121, 123 provide for overflow of wash solution from thewashing well 121 into the drain bore 123, the lower end of which isconnected via a fitting 127 (e.g., a SWAGELOK® fitting). The cylindricblock 117 of the wash tower 101 is surrounded by a jacket 133 containingresistance heating coils (not shown) connected to a source of electricpower by a connection 135. The heating coils transfer heat to thecylindric block 117 to heat the block and wash solution in the washingwell 121, as will be described later. The solution should be heated to asuitable temperature (e.g., about 170°-200° C.), such as temperaturesufficient to remove any coagulated reaction materials on the needle ofthe cannula 21. As shown in FIG. 2, the drain lines 107, 129 from thewash towers 101, 111 are connected to a suitable drain system includingflasks 137 for collecting waste. Valves 138 in the waste lines can beclosed to permit disconnection and emptying of the flasks 137. Afterreconnection of the flasks, valves 139 are opened to permit evacuationof any remaining vapor in the flasks by a means of a vacuum pump 140,following which valves 139 are closed and valves 138 opened toreestablish fluid communication between the flasks and their respectivecleaning towers 101, 111 without contaminating the inert environmentwithin the enclosure 3.

[0048] In the preferred embodiment, the cleaning apparatus 25 alsoincludes an ultrasonic device 141 (FIG. 3) having a central recess 143for receiving a cannula 21. This device generates ultrasonic waves whichmechanically vibrate the cannula as it is flushed with solvent toprovide an additional mechanism, if needed, for removing slurryparticles on the interior and exterior surfaces of the needle of thecannula. The ultrasonic device 141 can be used alone or in combinationwith one of the wash towers 101, 111. A suitable ultrasonic device 141is manufactured by Branson Ultrasonics Corporation of Danbury, Conn.,part number B3-R, and distributed by Cole-Parmer Instrument Company ofVernon Hills, Ill., under part number P-08849-00.

[0049] Referring now to FIGS. 9-11, each reactor module 9M comprises areactor block 151 of suitable metal mounted on a pair of legs 153secured to a base 155 which is fastened to a respective carriage plate67 b. The reactor block 151 is preferably mounted in a position spacedabove the base so that it is thermally isolated from the base. Eachreactor block 151 has two or more (e.g., eight) vessels therein formedby wells 163 each of which extends down from an upper surface of thereactor block and each of which has a central longitudinal axis Al whichis typically (but not necessarily) generally vertical. In the preferredembodiment, each well has a removable liner in the form of a reactionvial 165 for holding a reaction mixture to be processed. The reactionvial 165 may be of glass or other suitably chemically inert materialcapable of withstanding high-temperature chemical reactions. As usedherein, the term “vessel” broadly means any structure for confiningreaction materials in the reactor, including the walls defining the well163, and/or the vial 165 or other liner in the well containing thereaction materials. In the embodiment shown in FIG. 10, the reactionvial 165 has a height substantially less than the height of the well163, forming a head space 167 within the well above the vial, the headspace and interior of the vial combining to form what may be referred toas a reaction chamber. This chamber is sealed closed by a header plate169 releasably secured by suitable fasteners to the reactor block 151.

[0050] A stirrer mechanism, generally designated 171 in FIGS. 10 and 11,is provided for stirring the contents of each vessel. This mechanismpreferably comprises a stirrer in the form of a shaft 175 having amixing blade or paddle 177 thereon engageable with the contents of thevessel, and a magnetic drive 179 of the type described in theaforementioned U.S. application Ser. No. 09/548,848 for rotating thestirrer at speeds in the range of 0 to about 3000 rpm, and preferably ata speed in the range of about 200-2000, and most preferably at a speedin the range of about 1000-2000. The drive mechanism 179 is releasablycoupled to the shaft 175 by a quick-acting coupling, generallydesignated 181, which may be of the type disclosed in the aforementionedU.S. application Ser. No. 09/548,848, or in the aforementioned co-owned,pending application Ser. No. 60/255,716, filed Dec. 14, 2000. Themagnetic drives 179 of the various stirrer mechanisms 171 of the reactormodules 9M are powered by a drive system comprising a gear train 185(FIG. 11) releasably coupled to a stepper motor 187 by means of a keyand shaft slip connection 189, as best illustrated in FIG. 5. The motor187, in turn, is supported by brackets 191 fastened to the legs 153extending up from the base on opposite sides of the reactor block 151.The gear train 185 and drive mechanisms 179 are enclosed by a cover 195releasably secured to the header plate 169 on the reactor block 151. Thearrangement is such that the stepper motor 187 rotates the gears of thegear train 185 to drive the magnetic drives 179 to rotate the stirshafts 175 in the vessels of the reactor module.

[0051] It will be understood that the stirrer mechanisms 171 may berotated by other types of drive mechanisms. Also, each stirrer mechanismcan be rotated by an independent drive system so that the rotationalspeed of the stirrer can be varied independent of the speed of the otherstirrer mechanisms.

[0052] Referring to FIG. 11, a burst manifold 201 is secured to a spacerplate 203 attached to the bottom of the reactor block 151. The manifold201 houses a series of disks 205, each of which is mounted in a passage207 communicating with a respective well 163. In the event the pressurein a reaction chamber exceeds a predetermined pressure, the disk 205 isdesigned to rupture, which allows the chamber to vent into a ventpassage 209 in the manifold communicating with a suitable vent system.The rupture pressure should be somewhat above maximum expected reactionpressures. In preferred embodiments, the reaction pressures are greaterthan atmospheric, preferably at least about 15 psig, more preferably atleast about 50-100 psig, and yet more preferably up to about 500 psig ormore.

[0053] In accordance with one aspect of the present invention, eachreactor module 9M has a plurality of cannula passages 215 thereinextending between an exterior surface of the reactor block 151 and thewells 163 formed in the reactor block, preferably one cannula passage215 for each well. In the preferred embodiment shown in FIG. 10 and 12,each cannula passage is straight and extends at an angle from a locationadjacent the upper end of the reactor block 151 at one side thereof to arespective well 163 in the block, intersecting the side wall of the wellin the head space 167 above the upper end of the mixing vial 165 in thewell or, in the event a vial is not used, above the level of any liquidand/or solid reaction components in the well. The central longitudinalaxis A2 of the passage 215 is at an appropriate angle e relative to thecentral longitudinal axis A1 of the vessel, e.g., at a 25 degree angleoff vertical, assuming the axis of the vessel is vertical (although itis not necessarily so). While the passage 215 shown in the drawings isstraight, it will be understood that the passage need not be absolutelystraight. For example, if the portion of the cannula 21 to be insertedinto the passage is flexible or somewhat non-linear, the cannula passage215 could also assume non-linear configurations (e.g., an arcuateconfiguration). However, in the preferred embodiment, the cannulapassage is at least substantially straight, meaning that it issufficiently straight to accommodate a cannula needle of the type to bedescribed later in this specification.

[0054] The passage 215 is positioned so that when a respective cannula21 is inserted into and through the passage 215, the distal end of thecannula is positioned inside the vessel, preferably inside the reactionvial 165 if one is used, for delivery of reaction material from thecannula at an elevation above any liquids and/or solids in the vial, andin a generally downward direction so that the reaction material exitingthe cannula is delivered into the vial without contacting any surface ofthe vial, as will be discussed later. The size and cross-sectional shapeof the cannula passage 215 is not critical. By way of example, however,which is not intended to be limiting in any respect, the passage can beformed by a circular bore having a diameter which exceeds the outsidediameter of cannula 21 by about 0.032 in. The angle e of the cannulapassage 215 may also vary, depending on the spacing between adjacentreactor modules 9M, the height of the reactor module, the size of thevessels, and other factors. In the preferred embodiment, all cannulapassages 215 extend from an exterior surface of the reactor block 151 onthe same side of the block, but it will be understood that the cannulapassages for different wells 163 could extend from different sides ofthe reactor block without departing from the scope of this invention.

[0055] A sealing mechanism, generally designated 221 in FIG. 12, isprovided in each cannula passage 215 for maintaining the reaction vesselsealed against ambient conditions when the cannula is inserted into andwithdrawn from the cannula passage, thus preventing any substantialpressure losses if the pressure in the reaction vessel is positive, orany pressure gains if the pressure in the reaction vessel is negativewith respect to ambient pressure. As shown best in FIGS. 12-14, thesealing mechanism 221 is located in the passage 215 adjacent its upperend at the entry port thereof which is enlarged by a counterbore 225 toaccept the mechanism. The mechanism 221 includes a valve 227 movablebetween a closed position for closing the cannula passage 215 and anopen position permitting movement of the cannula through the passage,and a seal 229 in the passage sealingly engageable with the cannula 21when the valve 227 is in its open position. The valve 227 and seal 229may be separate elements or formed as a single unit. In the preferredembodiment, the valve and seal are fabricated as a single assembly ofthe type described in U.S. Pat. No. 4,954,149, incorporated herein byreference, owned by Merlin Instrument Company of Half Moon Bay, Calif.In this (FIG. 12) embodiment, the valve 227 has a body 231 molded fromsuitable material (e.g., Viton® fluorocarbon rubber) received in acounterbore 233 in the reactor body 151, a sealing ridge 235 extendingcircumferentially around the body 231 for sealing against the reactorbody, a central passage 237 through the body forming part of the cannulapassage 215, a duckbill valve comprising a pair of duckbill lips 241formed integrally with the valve body 231, and a metal spring 243 (e.g.,of hardened stainless steel) which biases the lips 241 together to closethe passage 237. The lips 241 are forced open against the bias of thespring by the distal end of the cannula 21 as it is inserted through thepassage 237 in the valve body (FIG. 13). The lips 241 have a sliding fitagainst the cannula as it is so inserted. The first-mentioned seal 229is an annular seal on the body immediately above the valve formed by theduckbill lips 241 on the side of the valve opposite the vial 165 in thewell. The annular seal 229 is sized for sliding sealing engagement withthe cannula 21 as the cannula is withdrawn from the reactor, since itmay take some very small period of time for the lips 241 of the duckbillvalve to close after the cannula is pulled past the lips. The sealingmechanism 221 is held in place by a nut 251 threaded in the counterbore225 in the reactor block 151 into engagement with a circular sealingridge (not shown) on the upper face of the valve body 231. As shown inFIG. 12, the nut 251 has a central bore 253 therethrough aligned withthe passage 237 through the valve body 231. The upper end of this borewhich constitutes the entry port of the cannula passage 25, is taperedto provide a lead-in 255 for the cannula.

[0056] A wiper assembly, generally indicated at 261, is providedadjacent the upper (inlet) end of each cannula passage 215 (see FIGS. 9and 12). The assembly 261 comprises a wiper frame 263 mounted on thereactor module 9M immediately above the inlets of the cannula passages215, a wiper member 265 overlying a leg 267 of the frame having one ormore openings 269 therein in registry with the upper entry end of thecannula passages 215, a clamp member 271 overlying the wiper member 265,and fasteners 275 (only one shown in FIG. 12) for tightening the clampmember 271 on the frame 263 to clamp the wiper member 265 in place. Thewiper member is of a material capable of being penetrated by the distalend of the needle of the cannula 21 and then wiping reaction materialoff the exterior surface of the needle as it is moved down into thecannula passage 215. The removal of reactant material before entry ofthe cannula into the cannula passages is important, especially whenhandling slurries containing small solid particles, since such particlescould interfere with the sealing mechanisms 221 in the passages 215. Onematerial found to be suitable as a wiper member is an expanded Teflon®gasket material sold by W.L. Gore & Associates, Inc. Other materials(e.g., silicone rubber) may also be used. Preferably, the wiper member265 comprises a single strip of material which extends the length of thereactor block 151 at one side of the block and overlies the openings 269at the upper ends of all cannula passages 215 in the block (see FIGS. 9and 12). Alternatively, the wiper member 265 can comprise separatepieces for the separate cannula passages 215. The wiper frame 263 isremovably mounted on the reactor block 215 so the wiper member 265 canbe easily replaced after each run. In the preferred embodiment, theframe 263 sits on pins (not shown) on the reactor block 151 and iseasily removed simply by lifting the frame off the pins.

[0057] Gas manifolds 281 extend along opposite sides of the reactorblock 151, as shown in FIGS. 9 and 10. Process gas lines 57 extendingfrom fittings 55 on the enclosure 31 communicate with one manifold (theright manifold as shown in FIG. 10) to provide for the delivery ofprocess gas (e.g., reactant gas such as ethylene or propylene) to thevessels in the reactor module 9M. Lines 57 extending from the fittings55 on the enclosure to the other (left) manifold 281 provide for thedelivery of quenching or inert gas (e.g., carbon dioxide) to the vesselsto terminate a reaction and/or to vent the gaseous contents of thevessel. Flow through the lines 57 to the manifolds 281 is controlled bysolenoid valves 285 mounted on the bore 155 immediately adjacent thereactor module (FIG. 4).

[0058] In general, the robot system 23 is a conventional three-axissystem providing translational movement along X, Y and Z axes (see FIGS.15 and 16), except that the system is modified as described hereinafterto provide for rotational movement about a fourth axis R, which mayintersect axis Z. The conventional three-axis system referred to may bea system commercially available from Cavro Scientific Instruments ofSunnyvale, Calif., Model No. 727633. Referring to FIG. 3, the robotsystem 23 in one embodiment comprises a horizontal track 301 mounted onthe enclosure 3 by brackets 303, left and right carriages 305 b, 305 amounted on the track for linear movement along the X axis, and left andright robot arms 307L, 307R extending from respective carriages. (Asreferred to herein, left and right is as viewed in FIGS. 1, 3, 15 and16.) An elongate rack 311 on each arm 307L, 307R carries a respectivecannula 21. The rack 311 is mounted for movement in a slot 313 in therobot arm along the Y axis, and is also engageable with a drive pinion(not shown) in the arm for movement along the Z axis. In accordance withanother aspect of this invention, the carriage 305L, 305R associatedwith each robot arm 307L, 307R is modified to provide for rotation ofthe arm about axis R. Since the left and right carriages may be ofsomewhat different construction, both will be described.

[0059] The construction of the right carriage 305R is shown in FIGS.17-19. The carriage comprises a slider 317 engageable in conventionalfashion with the track 301, a base 319 affixed to the slider, a shaft321 mounted on the base having a longitudinal axis A3 corresponding toaxis R, and a pivot block 325 mounted on the shaft for rotation on axisR. The pivot block 325 carries the right robot arm 307R and is rotatableby a power actuator which, in the preferred embodiment, is adouble-acting pneumatic cylinder 329R. The cylinder 329R is mounted on aplatform 331 pivotally secured at 333 in FIG. 19 to the pivot block 325and has a rod end having a clevis pivot connection 335 with a shaft 337extending from the base 319, the arrangement being such that theextension of the cylinder rod causes the pivot block 325 to rotate in afirst (clockwise) direction from the generally horizontal “home”position shown in FIG. 17 to the tilted position shown in FIG. 18, andretraction of the rod causes the pivot block to rotate in the opposite(counterclockwise) direction. During such extension and retraction, theplatform 331 pivots relative to the pivot block 325 and the clevisconnection 335 rotates on the shaft 337. Extension and retraction of thecylinder 329R is controlled by a suitable pneumatic system, one suchsystem being designated 341 in FIG. 2. In this embodiment, an inert gas(e.g., argon or nitrogen) is supplied to opposite ends of the cylinder329R by two lines 343, 345, the first of which (343) supplies gas at arelatively high pressure (e.g., 60 psig) to one end of the cylinder forextending the cylinder to rotate the pivot block 325 to its angled(tilted) position, and the second of which (345) supplies gas at a lowerpressure (e.g., 40 psig) to the opposite end of the cylinder. Both gaslines 343, 345 are connected to a suitable source 351 of high pressuregas (e.g., argon or other inert gas). Regulators 353 are used to controlthe pressure in the lines 343, 345. A solenoid valve 357 in line 343controls the supply of high pressure gas to the cylinder 329R. Bothlines contain orifices 361 adjacent the cylinder 329R to restrict theflow of gas to dampen the movement of the cylinder, and thus therotational movement of the pivot block 325 and robot arm 307R. When thesolenoid valve 357 is open to provide high pressure gas to the cylinder,the piston of the cylinder extends against the lower pressure gas torotate the pivot block 325. When the solenoid valve 357 is closed, gasis vented from the high-pressure end of the cylinder 329R, allowing thepiston to move in the opposite direction under the influence of thelower pressure gas to rotate the pivot block 325 in the oppositedirection. Other pneumatic circuits may be used. Similarly, other typesof power actuators may be used for rotating the pivot block 325.Further, other damping means may be used to dampen the rate of pivotalmovement of the pivot block 325 and robot arm 307R about axis R. Forexample, a suitable damping device could be positioned between the pivotblock 325 and the base 319.

[0060] The range of rotational movement of the pivot block 325 isdetermined by stops (see FIGS. 17 and 18). In the preferred embodiment,movement in the clockwise direction is determined by the location of afirst adjustable stop 365 on the base 319 engageable by a first stop 367on the pivot block 325, and rotational movement of the pivot block inthe counterclockwise direction is determined by the location of a secondadjustable stop 369 on the base engageable with a second stop 371 on thepivot block.

[0061] The first adjustable stop 365 comprises a damping cylinder 375mounted on the base 319 in a generally horizontal position, and a rod377 (FIG. 17) extending from the cylinder having an upper end engageableby the first stop 367 on the pivot block 325. The cylinder 375 has athreaded connection with the base 319 so that the cylinder may be movedalong its axis to adjust the axial position of the rod 377. A jamb nut(not shown) may be used to secure the cylinder in adjusted position. Thedamping cylinder 375 contains fluid movable through an optimallyadjustable orifice to damp movement of the rod 377 as it moves to itsfinal fixed position, as will be understood by those skilled in the art.The cylinder and rod are of conventional design. A suitable dampingcylinder 375 is commercially available from Humphrey of Kalamazoo,Mich., Part No. HKSH5X8.

[0062] The second adjustable stop 369 is similar to the first adjustablestop 365 described above except that the cylinder (designated 381) ismounted in a generally vertical position for engagement of its rod 383by the second stop 371 on the pivot block 325.

[0063] It will be understood, therefore, that the range of rotationalmovement of the pivot block 325 can be adjusted by setting the locationof the adjustable stops 365, 369 to the desired locations. In thepreferred embodiment, the range of motion is through a range of about 25degrees, preferably between a position in which the cannula 21 isvertical and one where the cannula is 25 degrees off vertical, althoughthis range may vary without departing from the scope of this invention.Whatever the range, the pivot block 325 in its tilted position shouldrotate the robot arm 307R to a position in which the cannula 21 is heldat an angle corresponding to the angle of the cannula passages 215 inthe reactors 9M so that the cannulas can be inserted through thepassages.

[0064] The range of rotational movement of the pivot block 325 can belimited in other ways without departing from the scope of thisinvention.

[0065] The left carriage 305L for the left robot arm 307L is shown inFIGS. 20-22. The construction of the left carriage is very similar tothe construction of the right carriage 307R, and corresponding parts aredesignated by the same reference numbers. However, there are somedifferences between the two carriages even though the left and rightrobot arms are mirror images of one another. This is because, in thepreferred embodiment shown in the drawings (e.g., FIG. 9), the entryports of the cannula passages 215 of the reactor modules 9M all face inthe same lateral direction, i.e., toward the left end of the dry box 3shown in FIG. 1. Another reason for the different construction is thepreference to maintain the R-axis of rotation of each robot arm 307L,307R in line with the Z-axis of travel to reduce the complexity of themotion control for the robot. In any event, the most significantdifference in construction is that, for the left carriage 305L, thepivot shaft 321 is on the opposite side of the base 319, and thecylinder 329 is mounted so that retraction of the cylinder causes thepivot block 325 (and the left robot arm 307L) to rotate from its homeposition shown in FIG. 20 to its angled position shown in FIG. 21, andextension of the cylinder causes the pivot block to rotate from itsangled position back to its home position.

[0066] It will be understood that the construction of the left and rightcarriages 305L, 305R could be different from that shown withoutdeparting from the scope of this invention.

[0067] A cannula 21 used in the apparatus of the present invention isshown in FIGS. 23-25. The cannula includes a hollow tubular reservoir391 having a central longitudinal axis A4, an outside diameter, aninside diameter defining a hollow interior 375, a proximal (upper) end397 and a distal (lower) end 399. The cannula also includes a long thinstraight tube 401 (hereinafter referred to as a “needle”) extendingcoaxially with respect to the reservoir 391. The needle 401 has anoutside diameter substantially less than the outside diameter of thereservoir 391, an inside diameter which defines a central flow passage403 extending the length of the needle, an open proximal (upper) end 405which communicates with the hollow interior 395 of the reservoir, alower distal end 407, and a port 409 adjacent the distal end which openslaterally (i.e., to the side) relative to the aforementioned axis. Theupper end 405 of the needle 401 is joined to the lower end 399 of thereservoir 391 by means of a bowl-shaped metal transition, generallydesignated 411, having a sloping, funnel-shaped interior side wall 413and a bottom 415 having a hole 417 therein for snugly receiving theupper end portion of the needle, the upper end 405 of the needle beingflush with the interior surface of the transition. The transition isjoined to the reservoir and the needle by welds indicated at 421 in FIG.23A. These weld areas, and the entire interior surface of the transitionand adjacent surfaces of the reservoir and needle, are polished to ahigh degree of smoothness so that the interior surfaces of thereservoir, transition and needle form a continuous expanse of smoothsurface area without crevices or other surface discontinuities whichmight trap particles or other material which could interfere withaspiration into the needle or delivery from the needle in accuratequantities. The exterior surfaces of the reservoir 391, transition 411and needle 401 should be similarly polished.

[0068] By way of example, the reservoir 391 is formed from metal,preferably stainless steel tubing having, for example, an outsidediameter in the range of about 0.05 to 0.50 in, more preferably in therange of about 0.05-0.25 in, and most preferably about 0.188 in.; aninside diameter in the range of about 0.02-0.45 in, and more preferablyabout 0.118 in.; and a length in the range of about 1.0-6.0 in, morepreferably about 2.0 in. The volume of the reservoir 391 should besubstantially greater than the largest volume of material to beaspirated into the cannula 21 (e.g., preferably in the range of about 10μl-5000 μl, more preferably in the range of about 25 μl-3500 μl, andmost preferably about 350 μl).

[0069] The needle 401 is preferably also formed from metal tubinghaving, for example, an outside diameter in the range of about 0.02-0.10in, and more preferably about 0.028 in.; an inside diameter in the rangeof about 0.01-0.09 in., and more preferably about 0.0155 in.; and alength in the range of about 1.5-5.0 in, more preferably in the range ofabout 2.0-4.0, and most preferably about 3.4 in. The port 409 of theneedle, shown best in FIG. 24, is generally oval in the shape of aracetrack and is sized to have a minimum dimension D1 substantiallylarger (e.g., four times larger) than the largest particle of materialto be handled by the cannula. For example, a port 409 having a minimumdimension of about 0.0155 has been found to be acceptable for handlingslurries containing silica particles averaging 10-100 microns indiameter. Other shapes and dimensions may be suitable, depending on thetype of material being handled. The transition 411 is preferably of thesame metal as the needle 401 and reservoir 391, e.g., stainless steel,and has a suitable axial length (e.g., preferably in the range of0.10-0.50 in., and more preferably about 0.215 in.) The exact shape ofthe transition is not believed to be critical, so long as the insidesurface of the transition is contoured for funneling material from thereservoir to the needle to provide for efficient flow between thereservoir and needle (e.g., no air pockets or other dead volume orspace). The interior surface of the transition 411 should also be smoothto minimize any discontinuities or other surface variations which wouldotherwise tend to trap material. In the preferred embodiment, theinterior wall 413 of the transition 411 is generally conical with anincluded angle ω in the range of about 20-70 degrees, and morepreferably about 30 degrees, although other angles of inclination mayalso be used. The upper end of the transition 411 is formed with anupwardly projecting annular shoulder 425 received in a shallowcounterbore 427 in the lower end 399 of the reservoir 391 to ensureproper registration between the two members when they are securedtogether, as by laser welding. The OD of the transition 411 ispreferably substantially the same as the OD of the reservoir 391, andthe ID of the transition at its upper end is preferably the same as theID of the reservoir at its lower end.

[0070] The cannula 21 can be fabricated as follows. The needle 401 ismade by bending the end of a length of straight metal tubing and cuttingthe distal end of the tubing along a line A-A (FIG. 25), parallel to theaxis A4 of the tubing, to form the laterally opening port 409. To insurethat the port 409 opens substantially downwardly when the needle isinserted in the cannula passage 215, the angle a between the cut lineA-A and the bend radius 429 should substantially correspond to the angleA of inclination of the passage 215. The proximal (upper) end 405 of thetube is then inserted into the hole 417 in the bottom of the transition411 and welded in position along weld lines 421 on the inside andoutside of the transition. The inside and outside surfaces of thetransition and welded areas of the needle are subjected to agrinding/polishing procedure to provide a smooth finish in which theupper end of the needle is flush with the inside surface of thetransition, and in which all surfaces and junctures are completelysmooth. The distal end 407 of the needle 401 at the port 409 are alsopolished. The transition 411 is then welded to the tubular reservoir391. A final polishing operation smooths the weld areas at the juncturebetween the transition 411 and the reservoir 391, and the inside andoutside surfaces of the reservoir.

[0071] The cannula 21 can be fabricated in other ways. However, it isimportant that the cannula needle have a laterally opening port so thatwhen the needle is inserted through the cannula passage 215 and into thereaction chamber, fluid reaction material (e.g., slurry material) isdelivered from the port in a downward direction onto the interior bottomsurface of vial 165 or the surface of the contents in the reaction vialrather than onto the side wall of the vial. Further, it is importantthat a reservoir be provided above the needle to insure that reactionmaterials aspirated into the needle are fully contained without backingup into the flow lines of the system.

[0072] A flow line 431 (e.g., flexible plastic tubing) is secured to theupper open end of the reservoir 391 by means of a fitting 433 having asealing connection with the upper end of the reservoir and the flow line(FIGS. 26 and 27). This connection is effected by means of a compressionnut 435 threadable on the fitting 433. The nut 435 is designed so thatwhen it is turned, it squeezes against the flow line 431 and reservoir391 to provide a sealing connection of the line to the reservoir for theflow of working fluid (e.g., solvent) between the pump 43 and thecannula 21, as occurs during operation of the system.

[0073] Again referring to FIGS. 26 and 27, each cannula 21 is mounted ona respective robot arm 307R, 307L by means of a mount comprising abracket 441 secured at its upper end to the elongate rack 311 extendingdown from the robot arm, and a cannula support 443 secured to thebracket 441 for supporting and stabilizing the cannula as it is moved.More particularly, the cannula support 443 comprises a yoke-like body445 which is mounted on locating pins 446 projecting forward from thebracket and secured in position to the bracket by suitable fasteners(e.g., socket-head cap screws, not shown). The body 445 has a verticalbore 447 through it for receiving the reservoir 391 of the cannulatherein, a pair of recesses 449 in the front face of the body 445exposing portions of the reservoir, a pair of clamping plates 451received in the recesses and engageable with the exposed portions of thereservoir, and clamping screws (not shown) extending through clearanceholes 453 in the clamping plates and threadable into the body 445. Theclamping screws are tightened to draw the clamping plates toward thebody to clamp the reservoir in fixed position against the body. Thecannula should be secured in a position wherein the port 409 at thedistal end 407 of the needle 401 faces in a generally downward directionwhen the cannula is in its fluid delivery position.

[0074] The cannula support 443 also includes a head 455 fixedly mountedon a pair of parallel guide rods 457 which are slidable in bushings (notshown) in bores of arms 463 extending laterally from opposite sides ofthe support body 445. The head 455 has a central bore 465 therein (FIG.28) sized for a close clearance fit with the needle 401 of the cannulaat a position intermediate the ends of the needle. The head 455 ismovable relative to the body 445 from a lowered position (shown in solidlines in FIG. 26 ) in which the head is spaced from the body forengagement with a more distal portion of the needle 401, and a raisedposition (shown in phantom lines) in which the head is closer to thebody for engagement with a more proximal portion of the needle to allowfor insertion of the said more distal portion of the needle into acannula passage 215. The head 455 and guide rods 457 affixed thereto arebiased by gravity toward the lowered position. A retaining ring (notshown) on at least one of the guide rods 457 is engageable with thesupport body 445 for limiting the downward movement of the head. Theclose clearance fit of the needle 401 in the bore 465 of the head (FIG.28) maintains the needle in the required precise angular position, andalso stabilizes the needle to prevent buckling of the needle in use, aswhen the needle is pushed to penetrate the sealing mechanism 221. (Thismechanism may be resistant to penetration if the pressures in thereactor chamber is large.) Preferably, the bore 465 in the head 455 issized to be about 0.001-0.010 in. larger than the OD of the needle 401,and more preferably about 0.004 in. larger.

[0075] The operation of the robot system 23, the various valves fordelivering gases to and from the reactor vessels, and other electroniccomponents of the system are under the control of a suitable systemprocessor and software (or firmware). Reference may be made to theaforementioned U.S. application Ser. No. 09/548,848 for more detail. Ingeneral, however, the robot system 23 is operable to use the left robotarm 307L to service one bank of reactor modules 9M (e.g., the left threemodules in FIGS. 1 and 2) and the right robot arm 307R to service theremaining modules (e.g., the right three modules in FIGS. 1 and 2).Using multiple robot arms to service different sections of the reactormatrix speeds set-up of the parallel reactor system and manipulationduring the course of the reactions. Alternatively, the robot systemcould have only one arm 307 to service all modules, or three robot armscould be used. When using multiple robot arms, different arms could bededicated to delivering different reaction materials to all or less thanall of the reactor modules. The precise locations of the variouscomponents of the reactor system (e.g., cannula passage 215 entry ports,wash towers 101, 111, ultrasonic cleaners 141, vial positions in theracks 17) are programmed into the robot system in a manner which will beunderstood by those skilled in the art.

[0076] The general operation of the system will now be described. First,vessels and stirrers are installed and the reactor covers 195 arereplaced and secured. Optionally, but preferably, a set of purgeprocedures is followed to purge all inlet lines, particularly thoseinlet lines 57 that will contain reactant gas. These purge proceduresmay not be necessary if the previous run left the reactor in a ready orpurged state. Generally, the purging is carried out so that all linesand reactor vessels contain a desired atmosphere or gas. In the deliveryor inlet lines, typically, a reactant gas may be used, such as ethylenegas, to ensure that no dead volumes or other gases are in the deliverylines.

[0077] Thereafter, liquid components are added to the reactor vessels.For example, if catalytic materials for a polymerization reaction are tobe characterized, the vessels may contain a solvent or diluent and otherliquid reagents (e.g., a liquid co-monomer, such as 1-octene, 1-hexeneor styrene, if desired). Suitable solvents may be polar or non-polar andinclude toluene and hexanes. The solvents loaded into the reactorvessels may be, but are not necessarily, the same solvents used in otherparts of the apparatus (e.g., the working fluid used in the syringepumps and the solvents used in the wash towers). Thereafter, thetemperature set point of the reaction is set and the temperature isallowed to stabilize. Then the reactors are charged with the atmosphericgas for the reaction, which may be an inert gas or reactant gas, inorder to bring the vessels to the desired operating pressure, which istypically in the range of from 0-500 psig. If the reaction atmosphere isa reactant gas (e.g., a gaseous monomer, such as ethylene), the liquidreagents are typically allowed to become saturated with the gaseousmonomer such that the reaction vessel contents reach an equilibriumpoint. In the example being followed (i.e., a catalyzed polymerizationreaction), a catalyst particle-containing fluid or slurry is theninjected into the vessels. If a catalyst is the particulate (i.e., asolid supported catalyst) then the catalyst (e.g., includingco-catalysts or activators) and non-catalyst reagents (e.g., scavengers)are added to the vessels. Preferably, the catalyst in slurry form is thelast component to be added to the reactor vessels.

[0078] Generally, as used herein, a slurry comprises at least twocomponents, including (1) a solid particulate and (2) a liquiddispersing medium or diluent. The particulate is preferably a solidcatalyst (e.g., a zeolite) or solid supported catalyst (e.g., anorganometallic complex supported on a solid support, such as alumina orsilica). Slurries of this type are known in the art. The amount ofcatalyst depends on the experimental design as discussed herein.Typically, the slurry contains a sufficient quantity of the liquiddiluent to disperse the solid particulate in a substantially homogenoussuspension with appropriate agitation as necessary. The diluent istypically not a solvent for the solid catalyst or solid supportedcatalyst, but may be a solvent for other reaction materials, such asmonomer or scavenger. The viscosity and density of the diluent can beselected to facilitate substantial homogeneity of the slurry uponagitation. As used herein, substantially homogeneous means that theparticulates are dispersed sufficiently in the diluent so that uponaspiration of a sample from the slurry, a consistent fraction ofparticulate is aspirated reproducibly to within scientificallyacceptable error. This can be judged, e.g., on the basis of polymerproductivity or catalyst efficiency. Slurry homogeneity allows foraspiration of a known volume of slurry, from which can be determined thequantity of catalyst that is being used in a particular reaction (e.g.,being injected into a reaction vessel according to the design of thecombinatorial or high throughput experiment). For example, 10 mg ofsolid supported catalyst combined with sufficient diluent to produce 1ml of slurry can provide for a catalyst injection of 1 mg for every 100μl that is aspirated into a cannula 21 from a homogenous slurry. Thus,determination of catalyst to be injected (on the basis of moles or mass)can be determined on the basis of known volumes in the cannula and/orother parts of the reactor system described herein. Also, in otherwords, the slurry for injection can be adjusted (e.g., in terms ofconcentration of solid supported catalyst in the slurry) to accommodatethe equipment in use (e.g., cannula volume) as well as the design of thecombinatorial or high throughput experiment.

[0079] The preparation of the slurry for injection is highly dependenton the exact chemistry in practice. Generally, slurries are prepared bymixing the particulate solid material and the liquid dispersing mediumor diluent and thereafter agitating, preferably swirling or vortexing,the mixture to form a substantially homogenous slurry in which theparticulate solid material is suspended in the liquid. If the reactorvessels are initially charged with a liquid solvent, the same solventmay be used as the liquid dispersing medium for slurry preparation. Manyfactors can be adjusted to accommodate different chemistries, includingthe timing of adding the liquid dispersing medium to the particulatesolid material to make the slurry, the ratio of the particulate solidmaterial to diluent, the intensity with which the slurry mixture isagitated (e.g., the rate of swirling or vortexing) during preparation,the rate of cannula insertion into and out of the slurry, and the sizeand shape of the vial from which the slurry is aspirated prior toinjection. In the case of catalytic slurries, some solid catalysts andsome solid supports of supported catalysts are fragile and may degradeas a result of agitation (e.g., in terms of particle size or shape) orthe time for slurry preparation may be so long that the liquiddispersing medium will evaporate, thereby changing the concentration ofthe catalyst in the slurry from that desired by the experimental design.Thus, in one preferred embodiment, the slurry is prepared within alimited time prior to injection, for example less than 90 minutes priorto injection, more preferably not more than 45 minutes prior toinjection, more preferably not more than 10 minutes prior to injection,still more preferably not more than 5 minutes prior to injection andespecially not more than 1 minute prior to injection. Depending on thespeed set for the robots, etc., slurry may be prepared by mixing theparticulate solid material and the liquid dispersing medium within about30 seconds prior to injection to the reactor vessel, as describedherein. Other factors that can be adjusted include the intensity ofagitation of the slurry mixture. The rate of swirling or vortexing ofthe slurry necessary to achieve a substantially homogeneous slurrydepends on the concentration of the particulate solid material in theliquid dispersing medium and the volume and shape of the mixing vial. Ingeneral, the higher the concentration of solid particles in the slurry,then the higher the vortexing rate necessary to ensure a substantiallyhomogeneous slurry. Similarly, the lower the concentration of solidparticles in the slurry, the lower the vortexing rate should be.Examples of suitable slurry vortexing rates include from about 100 rpmto about 1300 rpm. Mixing vial sizes include 20 ml, 8 ml, and 1 ml.

[0080] For a catalytic reaction in which the catalyst is on a solidsupport, in order to prepare the slurry, the solid supported catalyst isfirst weighed, with the weight being used to calculate the amount ofliquid dispersion medium that is added to the supported catalyst toprepare the slurry for injection. The preparation of the slurry forinjection can be important with respect to the size of the cannula,since the cannula can accommodate only a limited amount of slurry. Thus,it is important to calculate the concentration of the slurry, thedesired catalyst amount on the support (e.g., silica) and then thedesired amount of liquid dispersing medium.

[0081] To initiate a typical run of reactions, the orbital shakers 13are actuated to shake the racks 17 containing the vials and agitate theslurry materials contained therein to provide a substantiallyhomogeneous slurry. The robot system is then actuated to move thecannulas to positions in which the desired quantities of slurry materialare aspirated from vials in respective racks on the shakers, the leftcannula 21 (as viewed in FIG. 1) aspirating from one or more vials inthe left rack 17 and the right cannula 21 aspirating from one or morevials in the right rack 17. During aspiration, the cannulas arepreferably in a vertical position and the shakers are preferably inoperation to agitate the slurry and ensure that the slurry aspiratedinto the cannula is substantially homogenous. When the cannula 21 isentering the vortexing slurry, the cannula speed along the Z axis of therobot is slowed down so that the cannula entering the vortexing slurrydoes not substantially disturb the homogeneous slurry. The cannula ispreferably paused from about 1-2 sec. in the vortexing slurry prior toaspiration in order to ensure that a substantially homogeneous slurry isaspirated into the cannula. Also, prior to aspiration, the speed ofaspiration is slowed (e.g., by slowing the aspiration rate of thesyringe pump 43) to avoid particle selectivity or other issues thatmight impact the homogeneity of the slurry that is aspirated into thecannula. Thereafter, the desired volume of slurry is aspirated into thecannula.

[0082] In the preferred embodiment, after aspiration of an appropriatequantity of slurry into a cannula 21 is complete, the robot system 23moves the cannula to aspirate a small volume of barrier liquid (e.g.,30-50 μl of optionally the same liquid charged to the reactor vessels)into the tip of the needle 401. The robot system is then operated tolift the cannula along the Z-axis of the respective robot arm 307L, 307Rto a height sufficient to clear the reactor modules 9M; the poweractuator 329 is operated to rotate the robot arm on its R-axis to tiltthe cannula to its fluid-delivery angle (e.g., 25°); and the cannula ismoved along X and/or Y-axes to a position in which the needle is readyfor insertion into the cannula passage 215 leading to the first vesselto be loaded with slurry, as shown in FIG. 12. The cannula is held inthis position for a short dwell period (e.g., 1-2 seconds) sufficient toallow any vibratory or harmonic movement of the needle to cease,following which the angled cannula is moved along the Z axis of theelongate rack 311 to cause the needle 401 to penetrate the wiper member265 to wipe any slurry material off the outside of the needle. Theneedle continues to advance into the entry port of the cannula passage215 and through the annular seal 229 to a position (FIG. 13) immediatelyupstream of the duckbill valve lips 241, where the advance of the needle401 is paused while the robot is signaled to increase the speed of theneedle 401 along the Z-axis of the rack 311. The syringe flow rate isalso increased. Alternatively, the syringe flow could be increased afterthe liquid barrier has been aspirated. In either event, after a dwell inthe position of FIG. 13, the needle is pushed forward at a relativelyhigh speed through the valve, forcing the lips 241 of the duckbill valveapart, and down through the passage 215 to the fluid delivery ordispensing position shown in FIGS. 10 and 14. As the needle approachesits dispensing position, the head 455 of the cannula support 443 engagesthe wiper member frame 263 and remains in that position as the needlecontinues to advance to the position shown in FIG. 10 where the distalend of the needle 401 is disposed inside the vial 165 at a level abovethe contents of the vial, and the port 409 in the needle faces generallydownward. The high speed of the needle 401 in combination with the smallvolume of barrier liquid in the tip of the needle and high syringe flowrate helps to avoid possible reaction from occurring in the cannula(e.g., in an embodiment where the slurry comprises a catalyst).

[0083] With the needle 401 in its FIG. 10 delivery or dispensingposition, solvent is pumped into the cannula 21 through the solvent line431 to force the small volume of barrier liquid and the predeterminedquantity of slurry material from the cannula directly into the vial 165.A predetermined quantity of chaser solvent is also dispensed in anamount sufficient to ensure that the slurry is effectively transferredto the vessel. Preferably, slurry preparation and the speed with whichthe robot system manipulates the cannula are controlled such that theslurry delivered to the vial remains substantially homogenous. In anespecially preferred embodiment, the slurry is delivered to the vialwithin 60 seconds of aspirating the slurry into the cannula.

[0084] Because the contents of the vessel are already under pressure,the slurry material must be delivered from the cannula at a pressuregreater than the vessel pressure. Typical reaction pressures vary fromabout ambient to 500 psig, and more preferably from about 50-300 psig,so at least some of the syringe pumps 43 (e.g., pumps 43 a) should havethe capability of generating a delivery pressure of up to 500 psig orgreater. Since the port 409 at the distal end of the needle 401 isfacing down, the slurry preferably does not contact or accumulate on theside walls of the vial 165 but rather is deposited on the surface of thecontents in the bottom of the vial where it can be properly mixed.Following delivery of the slurry material to the vial, the robot isoperable to withdraw the distal end of the needle 401 at high speed pastthe lips 241 of the duckbill valve to the position shown in FIG. 13between the lips 241 and the seal 229. The needle is held in thisposition for a short dwell period (e.g., 1-2 seconds) sufficient toenable the lips 241 of the valve to close and for the robot speed alongthe Z-axis of the rack to be reduced to a slower speed (i.e., the robotarm speed along the Z-axis is reset at this point to normal). Duringthis time the annular seal 229 is in sealing engagement with the needle401 to prevent any substantial leakage past the lips while they areclosing. The robot then moves the needle at the slower speed to aposition where it is completely withdrawn from the cannula passage andthe cannula is again at a height sufficient to clear the reactormodules. As the needle 401 withdraws from the cannula passage 215, thehead 455 of the cannula support 443 returns to its needle supportingposition shown in solid lines in FIG. 26.

[0085] After each aspiration into the cannula 21 and after each deliveryfrom the cannula, the cannula is preferably moved to the cleaningapparatus 25 and cleaned for several reasons. First, cleaning avoidscross-contamination of materials. Second, small particles (e.g., silicaparticles) which might otherwise interfere with or damage the reactionequipment are removed. And third, cleaning removes any build-up ofpolymer material on the needle 401 adjacent the port 409. (Somepolymerization may occur in the needle prior to dispensing, when theneedle is first exposed to reactant gas in the cannula passage.) If suchbuild-up is not removed, it could interfere with the delivery ofmaterial from the cannula and subsequent aspirations into the needle.Prior to insertion of a cannula into the appropriate wash tower 101, 111and/or ultrasonic cleaning device 141, the power cylinder 329 of arespective robot is actuated to rotate the robot arm 307L, 307R to itshome (or non-tilted) position in which the needle is vertical. Theneedle is then lowered for cleaning.

[0086] The robot system 23 is operated to move the cannula 21 back tothe rack 17 containing the slurry source followed by aspiration anddelivery of slurry to a second and subsequent vessels as necessary toload the reactor. Although the same slurry can be delivered to each ofthe vessels, it may be desired in some reaction protocols to deliver asecond slurry that differs in composition from the first slurry to atleast some of the remaining vessels in the reactor. The second slurrymay differ in composition in terms of solid particulate concentrationand/or the solid and liquid components of the slurry. For a single runof the reactor, there can be as many slurries as there are reactionvessels such that there may be 1, 2, 8, 16, 24 or 48 of different slurrycompositions.

[0087] It will be understood that the two robot arms 307L, 307R moveindependent of one another to carry out the dispensing process in themost efficient manner. As noted previously, the left robot arm typicallyservices the left bank of reactor modules and the right arm the rightbank of modules. Alternatively, one robot arm could be used to serviceall reactors. The speed at which the robots move the cannulas may alsovary to reduce the time needed to load the vessels. For example, thecannula 21 may be moved at higher speeds when larger distances are beingtraversed, and at slower speeds at other times, as when the cannula isapproaching various destinations and during the initial stages of needleinsertion into a cannula passage 215.

[0088] After the vessels have been loaded, the reactions are monitoredfor a desired interval of time or reaction stage or until the reactionsare considered to be finished, following which quenching gas (e.g., CO₂)is delivered to the vessels through lines 57 to terminate the reaction.After the reaction is completed, and prior to removing samples andvessels, appropriate venting procedures should be followed to ensurethat there is no loss of product through the vent lines. Specifically,if venting of the reaction vessels is too fast, the solid supportedcatalyst or other particulate materials (e.g., such as polymerparticles) may vent through the vent lines 57. Venting procedures mayinclude slow venting (e.g., vent valve cycling) and/or inert gas purging(e.g., argon or nitrogen). After the appropriate venting procedures arecomplete, the reactor covers 195 are removed to allow removal of thereaction samples and replacement of the removable vials and stirrers175.

[0089] In a preferred embodiment, the reaction vials 165 used in thereactor modules 9M should have a cross-sectional shape corresponding tothe cross-sectional shape of the wells 163 (e.g, circular), a volumesomewhat greater than the total volume of reaction materials and/orproducts to be contained by a vessel, and a height such that when thevial is placed in a well 163, the rim of the vial is at an elevationbelow where the cannula passage 215 enters the well. Preferably, theopen upper end of the reaction vial is positioned for receiving thedistal end of the needle 401 in its delivery or dispensing position,with the port 409 of the needle located inside the vial at an elevationbelow the upper end of the vial and facing downward. Thus, the height ofthe vial will vary depending on various factors, including the angle ofthe cannula passage 215, the reactor height, the depth of the well 163,and other factors. In the preferred embodiment, the vial has a roundedbottom and a cylindric side wall extending up from the bottom andterminating in a rim defining an open upper end of the vessel. For usein a reactor block of the type shown in FIG. 10, the side wall of thereaction vial has an inside diameter in the range of about 0.5-2.5 in.,more preferably in the range of about 0.5-0.75 in., and most preferablyabout 0.609 in.; the vial has an overall height in the range of about1.0-4.0 in., more preferably in the range of about 1.5-3.0 in., and mostpreferably about 2.15 in; and the vial defines a volume in the range ofabout 5-200 ml, and preferably in the range of about 5-20 ml, and mostpreferably about 10 ml.

[0090] In the event there is a need or desire to move, remove, and/orreplace one or more of the reactor modules 9M, as during a maintenanceprocedure, the carriage extension 83 is disconnected from the fixture 85on the table 3 by disconnecting the master locking device 81. Thisdisconnection triggers a shut-off switch which renders the robot system23 inoperable. Disconnection of device 81 allows all of the carriageplates 67 to be moved together as a unit along the rails 61. If desired,one or more of the other carriage plate locking devices 75 may bereleased to disconnect the appropriate carriage plates 67 from oneanother to allow the plates to be slidably moved relative to one anotheralong the rails 61 and the reactor modules 9M to be separated forconvenient service or rearrangement of the reactor matrix. After themodules are serviced and/or rearranged, the carriage plates 67 arereconnected and the carriage extension 83 reconnected to the tablefixture 85 to render the robot operable.

[0091] The parallel reactor system 1 described above can also be used todeliver low boiling reaction materials (i.e., substances which wouldnormally be in the gas phase at ambient temperature and pressure) to thevessels in the form of liquid phase condensates. This feature isillustrated in the schematic of FIG. 29. Thus, the reaction material inthis embodiment will have a boiling point no greater than about ambienttemperature at a pressure of about one atmosphere. Examples of such lowboiling reaction materials include 1,3 butadiene, propylene, vinylchloride and isobutlyene used in polymerization reactions, as well asmethyl chloride and isobutane.

[0092] The system 1 is modified to include a delivery system generallydesignated 501, for delivering the liquid reaction material condensateto the inlet port of a cannula, generally designated 505, mounted on oneof the robot arms 307L, 307R. The delivery system 501 comprises a source507 of the condensate and a flow path generally designated 509 from thecondensate source to the inlet port of the cannula 505. The condensatesource 507 can be located inside or outside the enclosure 3. Preferably,the condensate source is maintained at a pressure at least as great asthe vapor pressure of the reaction material. That is, the condensatesource comprises condensed gaseous reaction material under pressure. Byway of example only, the condensate source 507 may be a pressurizedcylinder containing a saturated vapor of the reaction material inequilibrium with liquid reaction material condensate at ambienttemperature (e.g., 25° C.). The cylinder (or other source) is adaptedfor the delivery of the condensed liquid phase reaction material intothe flow path, as by mounting the cylinder in an inverted position(i.e., such that the liquid level in the cylinder is above the outletport through which the condensate is removed from the cylinder), or byequipping the cylinder with a dip tube (the vapor pressure of thesaturated vapor being sufficient to force liquid condensate up the diptube and out of the cylinder). Flow of liquid reaction materialcondensate from the cylinder 507 is controlled by suitable valving 531which may be operated manually or automatically by a valve controllerunder the control of the system processor 527. A suitable mechanism(e.g., liquid level sensor) for indicating the amount of liquidcondensate remaining in the cylinder or other source 507 may also beprovided.

[0093] The delivery system further comprises a pump 511 in the flow path509 for pumping the condensate to the cannula. In one embodiment, thispump 511 may be a syringe pump similar to the smaller volume syringepump 43 b previously described. Other pumps may also be used. The flowpath 509 includes a flow line 515 connecting the outlet part of thecondensate source 507 to the intake of the pump 511 and a flow line 517connecting the output of the pump to the inlet port of the cannula 505.A solenoid-operated control valve 521 in the flow line 517 upstream ofand adjacent the inlet port of the cannula 505 is adapted to open anddeliver a quantity of pressurized condensate to the cannula. Theoperation of this valve is controlled by a valve controller 525 underthe control of the system processor 527.

[0094] Preferably, the delivery system 501 also includes a condenser,generally designated 535, downstream of the condensate source 507 forcooling the condensate in the flow path 509. The condenser 535 ispositioned in heat transfer relation with at least a portion of the flowline 515 between the condensate source 507 and the pump 511. Atemperature controller 537 is provided for controlling the temperatureof the condenser 535. A check valve 541 in the flow line 515 upstreamfrom the condenser 535 prevents backflow from the condenser to thecondensate source 507.

[0095] As best shown in FIGS. 30 and 31, the condenser 535 comprises abase 545 with a peripheral wall 547 extending up from the base, and aseries of components mounted on the base inside the wall, including athermoelectric assembly, generally designated 549, for cooling (andheating, if necessary) one or more flow lines 515 from the cylinder(s)or other condensate source 507, a heat sink 551 and a fan 553. Thethermoelectric assembly 549 comprises a pair of upper and lower metal(e.g., copper or aluminum) heat transfer plates 557, 559 having matinggrooves for receiving the gas flow line 515 (or lines if more than oneis provided), a thermoelectric device 569 for cooling (and heating, ifnecessary) the heat transfer plates, and suitable fasteners (not shown)for clamping the thermoelectric device and heat transfer plates togetherwith the flow line(s) 515 in heat transfer contact with the heattransfer plates and the upper heat transfer plate 557 in heat transfercontact with the thermoelectric device 569. The entire thermoelectricassembly 549 is thermally insulated by upper and lower insulatingmembers 565, 571 of thermal insulating material (e.g., calcium silicateor other thermal insulating material). The lower insulating member 571has an upwardly extending rim 573 defining a cavity for receiving thethermoelectric assembly 549. The upper insulating member 565 overliesthe upper heat transfer plate 569 and surrounds the thermoelectricdevice 557. A cover plate 575 is secured to the peripheral wall 547 ofthe base 545 to enclose the thermoelectric assembly 549 and insulatingmembers 565, 571. The flow line(s) 515 extends out through notches 577formed in the rim 573 of the lower insulating member 571 and theupstanding wall 547 of the base 545. The thermoelectric device 569functions to cool the reaction material in the flow line 515 (or lines)to a temperature sufficient to ensure that gaseous reaction material iscondensed to (or remains condensed in) liquid form, thereby avoidingbubbles and pockets of vaporized gas which might interfere with thedelivery of accurate quantities of material to the cannula. One suchthermoelectric device is commercially available from TellurexCorporation of Traverse City, Mich., part No. C1-14-63-165. Although itis preferred that the reaction material withdrawn from the condensatesource and passing through flow line 515 be in liquid form, it should beunderstood the reaction material may be in gaseous form at its sourceand condensed to liquid form upon cooling in the condenser.

[0096] The temperature controller 537 for controlling the temperature ofthe thermoelectric device 569 may be of any suitable type, such as anassembly including a thermocouple for sensing the temperature of one ofthe heat transfer plates 557, 559 (e.g., the lower plate), a display fordisplaying the temperature, and a variable DC power supply (e.g., a 0-30VDC , 0-6 A power supply). In this embodiment, DC power is applied tothe thermoelectric device 569 to cool the heat transfer plates 557, 559and gas line(s). While maintaining a constant voltage, the current maybe varied until a desired temperature is achieved, as indicated by thedisplay, using known performance characteristics of the thermoelectricdevice as a guide. An automatic temperature controller comprising athermostatic controller for cycling the thermoelectric device 569 on andoff as needed may also be used.

[0097] It will be understood that other chilling mechanisms could beused to cool the reaction materials to condense or maintain them inliquid (condensed) form. For example, if a chilled coolant system isused to cool the reactor modules 9M, the coolant from the same systemcould be used in a condenser to cool a portion of the flow line(s) 515.

[0098] As shown best in FIGS. 32-36, the cannula mount and supportmechanisms, generally designated 581 and 583, respectively, are modifiedto accommodate the delivery of reaction material condensate to and fromthe cannula 505. The cannula 505 itself comprises a needle 591 attached(e.g., laser welded) at its upper end to a connector generallydesignated 593. In the embodiment shown in FIGS. 36 and 38, the needle591 is formed from straight tubing to have an open upper end 595,constituting an inlet port, and an axial passage 597 through the needleterminating at a lower (distal) end 598, defining an outlet port. Theoutlet port 598 faces axially (rather than laterally as in the slurryneedle 401) and is chamfered as indicated at 599 at an angle A (e.g., 65degrees). The dimensions of the needle 591 are similar to those of theslurry needle 401, i.e., the needle 591 may have an outside diameter inthe range of about 0.020-0.10 in, and more preferably about 0.028 in.,an inside diameter in the range of about 0.01-0.09 in, more preferablyabout 0.0155 in., and a length in the range of about 1.5-5.0 in, morepreferably in the range of about 2.0-4.0, and most preferably about 3.4in.

[0099] The connector 593 has a generally cylindric body 601 (FIG. 37 and38) with a central passage 603 therethrough in fluid communication withthe inlet port 595 of the needle 591. The connector passage 603 iscounterbored as indicated at 605 in FIG. 38 for receiving the upper endof the needle so that the ID of the needle is substantially the same asthe ID of the passage 603. The upper portion of the connector body isformed with external threads 607 for threaded connection to the controlvalve 521, as will be described hereinafter. The lower portion of theconnector body 601 is formed with opposing wrench flats 609 (only oneshown in FIG. 37) to facilitate tightening of the connector in the valve521. For ease of manufacture, the OD of the lower portion of theconnector body 601 is the same as the OD of the upper portion of thebody at the root of the threads 607 thereon. The needle 591 andconnector 593 are preferably of the same material (e.g., 304 stainlesssteel) as the cannulas 21 used for slurry injection.

[0100] In particular, the cannula mount 581 comprises a rectangularmounting block 615 attached to a bracket 617 (similar to bracket 441previously described) by fasteners 619 (FIG. 33). The control valve 521is received in a recess in the block and releasably secured to the blockby fasteners 621 (FIGS. 34 and 34A). The control valve 521 has a firstbore 625 therein which receives a fitting 627 for attaching thecondensate flow line 509 to the valve, and a second bore 631 in fluidcommunication with the first by suitable passaging (not shown) in thevalve. In one embodiment, the valve 521 has a movable solenoid operatedvalve member (not shown) for opening and closing this passaging tocontrol the flow of condensate to the cannula 505. The second bore 631of the valve 521 is tapped for threadably receiving the upper threadedportion of the cannula connector 593. The upper end of the cannulaconnecter body 593 is of reduced diameter, as indicated at 635 in FIGS.34A and 38, for sealingly engaging a sealing gasket 637 in the bore 631of the control valve to prevent leakage.

[0101] In order to maintain the liquid reaction material condensate inthe liquid phase upon being delivered into the vessels, the reactionmixtures within the vessels are maintained at a pressure in excess ofthe vapor pressure of the condensate at the temperature conditionsprevailing in the vessels. For example, in the case of propylenecondensate, the vessels may be pressurized to a pressure of 500 psig ormore. Accordingly, the delivery system 501 including the control valve521 must be operable to deliver pressurized condensate at pressuresexceeding these vessel reaction pressures and to accommodate substantialpressure differentials across the valve, noting in this regard that thepressure of the condensed gas on the upstream side of the valve when thevalve is closed is typically relatively low (e.g., at about the vaporpressure of the condensed gas, which is about 36 psig at ambienttemperature for butadiene and about 154 psig at ambient temperature forpropylene). A solenoid control valve suitable for use in the system ismanufactured by Bio/Chem Valve Inc. of Boonton, N.J., Part No.100T2-PP493.

[0102] The cannula support mechanism 583 for the condensed gas needle591 is similar to the support mechanism 443 for the slurry needle 401,comprising a head 641 affixed to guide rods 643 slidable in bushings 645mounted in parallel bores 647 in the mounting block 615 (FIG. 34A).However, in this embodiment, the head 641 is provided with a larger,longer bore 651 for accommodating the larger diameter of the connector593. The lower end portion of the connector body 601 has a clearance fitinside this bore 651 to permit movement of the head 641 toward and awayfrom the mounting block 615. The lower end of the head 641 has a guidehole 655 therein having a close clearance fit with the OD of the needle591 for supporting it in precise position to ensure proper entry intothe cannula passages 215 and prevents buckling of the needle. The closeclearance fit may be the same as the fit of the slurry needle 401 in thebore 465 of head 455.

[0103] In the event a liquid reaction material condensate is to bedelivered to one or more vessels, and assuming the flow lines 515, 517from the condensate source 507 to the solenoid valve 521 are filled withliquid condensate, the solenoid valve is maintained in a closed positionuntil the needle 591 of the cannula 505 is inserted in a cannula passage215 to the stated fluid delivery (dispensing) position in which thedistal end of the needle is positioned in the reaction vial 165 as shownin FIG. 10. The solenoid valve 521 is then opened and the syringe pump511 operated to deliver a measured quantity of pressurized condensate tothe vessel. After delivery, the control valve 521 is closed and theneedle 591 withdrawn in the manner described above. Upon withdrawal, thecondensate downstream from the control valve 521 will vaporize andescape into the enclosure. To minimize this waste, the needle passage597 should be small in diameter, and the overall length of the flow path509 between the valve shut-off member of the control valve 521 and theoutlet port 598 of the needle 591 should be as short as practical. Forexample, in the preferred embodiment, the length of this passaging isabout 4.12 in. To prepare for delivery of liquid reaction materialcondensate to the next vessel, the syringe pump 511 is operated toaspirate additional liquid into the syringe of the pump from thecondensate source 507. The flow rate of condensed gas from the source507 to the syringe pump 511 and from the syringe pump to the cannula 505is preferably controlled to avoid cavitation and substantial pressuredrops which could cause vaporization of the reaction materialcondensate. For condensed propylene and butadiene gases, for example apreferred flow rate is up to 50 μl/sec., and more preferably in therange of 20-30 μl/sec.

[0104] Fluid waste generated during the course of the procedure (asduring a line purge and/or pump priming process) is delivered to asuitable waste receptacle 661, which may be a closed container having avent line 665 with a bleed valve 663 in it (FIG. 29). The receptacle 661may be provided with a cannula passage and a sealing mechanism in thecannula passage similar to the sealing mechanism 221 previouslydescribed. The cannula 505 is inserted into the passage, through thesealing mechanism, and any waste fluid is then pumped into thereceptacle without contaminating the glove box 3. Vapor in thereceptacle can be vented into line 665 by opening the bleed valve 663.

[0105] To avoid interference between the control valve 521 and thereactor module 9M during delivery, it may be necessary to rotate thebracket 617 90° from the position shown in FIG. 9 for the slurry cannula21. By rotating the bracket 617 in this manner, the longitudinal axis ofthe valve 521 extends generally parallel to the length of the reactormodule 9M, rather than perpendicular to it, thereby avoiding anyinterference which might otherwise result.

[0106] If necessary, the parallel reactor system 1 described can bemodified so that both cannulas are dedicated to the delivery of liquidreaction material condensate.

[0107] It will be observed from the foregoing that the parallel reactorapparatus of the present invention represents an advance over priorsystems. The system can be used to deliver hard-to-handle (e.g.,“sticky”) slurry materials. For example, as discussed herein, solidsupported catalyst particle size may be so small as to be considered“catalyst fines” or other characterizations that are typically used inindustry. At these particle sizes, reactor or equipment fouling ispossible. One of the benefits of this invention is that such fouling isminimized while still providing for the delivery of accurate volumes tothe reactor vessels in an efficient, fully automated manner, and atpressures other than ambient, if desired. Further, the system can alsobe used to deliver accurate quantities of a liquid reaction materialwhich would normally be in gaseous form at ambient temperatures. Becausethe condensable gas is maintained in liquid form by the combination ofpressure and limited cooling (e.g., by the condenser), there is no needto cool the reactor modules 9M or other equipment to the extremely coldtemperatures which would otherwise be necessary to condense the gas.Also, the system of the present invention provides for the cooling ofdifferent reaction materials to different temperatures, as needed,independent of any cooling of the reactor modules. Such cooling can beadjusted according to the reaction material being handled simply byadjusting the temperature of the thermoelectric device 569 in thecondenser 535. The cooling can also be adjusted to take into account thelength of the flow path 509, the time interval between injections, andother factors which affect the temperature of the reaction materialsprior to injection. The thermoelectric device can also be used todeliver heat to the flow line(s) to heat the reaction materials therein.

[0108] When introducing elements of the present invention or thepreferred embodiment(s) thereof, the articles “a”, “an”, “the” and“said” are intended to mean that there are one or more of the elements.The terms “comprising”, “including” and “having” are intended to beinclusive and mean that there may be additional elements other than thelisted elements.

[0109] The following example is simply intended to further illustrateand explain the present invention. This invention, therefore, should notbe limited to any of the details in this example.

EXAMPLE

[0110] In general, with the reactor modules 9M in a benign state, andthe reactor covers 195 removed, reaction vials 165 are inserted in thereactor wells 163. Disposable stirrers 175 are attached to the drivers179 and checked to ensure that the coupling 181 is engaged. Before thecovers 195 are re-secured, a metal tool is used to push each vial allthe way to the bottom of the reactor well 163, ensuring the vial is notobstructing the cannula passage 215. After the vials are verified to bein the correct position, the reactor covers 195 are secured to thereactor modules. Purge routines are run as defined earlier.

[0111] Experimental library design is supplied, which specifies reactantcomponents, quantities as well as database storage and retrievalparameters. For a standard catalyzed polymerization reaction, the robotsystem 23 is instructed to add to each reaction vial 165 200 μl ofliquid co-monomer 1-octene, followed by 4500 μl of hexane solvent, withthe left arm 307L of the robot servicing the left 3 modules 9M of thereactor and the right arm 307R of the robot system servicing the right 3modules of the reactor (see FIG. 1). While adding solvent andco-monomer, syringe flow rates are set to initial values of:

[0112] Start Speed: 100 μl/s

[0113] Top Speed: 300 μl/s

[0114] Cutoff Speed: 100 μl/s

[0115] For each X, Y and Z movement, there are 3 speeds for each robotarm 307 and, in this experiment, those speeds are the same for the rightand left arms of the robot system. These speeds are set to have thefollowing initial values:

[0116] Start speed: X=11.17 mm/sec, Y=28.11 mm/sec., and Z=9.8 mm/sec.

[0117] End speed: X=893.6 mm/sec, Y=568.8 mm/sec., and Z=196 mm/sec.

[0118] Acceleration: X=900 mm/sec², Y=800 mm/sec², and Z=500 mm/sec².

[0119] Once these reagents are added, the temperature is set to thespecified temperature from the experimental design, which in this caseis 85° C. Simultaneously, the stirrers 175 are activated to stir attheir desired RPM, which is 800 RPM. The temperatures in the reactionchambers of the reactor modules 9M are allowed to stabilize to their setpoint(s). Upon stabilization, each reaction chamber is charged withethylene gas at a pressure of about 100 psig, with the uptake ofethylene being monitored. After saturation of the solvent with ethylene(which takes an average of about 10 minutes), non-catalyst and catalystmaterial can be added to each reaction chamber. For example, 200 μ1 ofMMAO (modified methylamumoxane) can be added as a scavenger, followed by500 μl of additional hexane solvent acting as a chaser to flush thecannula 21. (Note that this entire process is automated with the robotsystem 23). During aspiration of the MMAO and hexane, the initialsyringe flow rates are used. During movements between the reactorchambers and reagents, the stated initial robot arm speeds are used.Once the cannula 21 has reached the position shown in FIG. 12, the armspeed is slowed down to have a Z acceleration component of 250 mm/sec²,allowing the needle 401 to pierce the wiper member 265. This arm speedis used throughout this portion of the addition sequence. When thecannula reaches the fluid delivery the position shown in FIG. 14, thesyringe flow rate is changed to 100 μl/s (start), 400 μl/s (stop), 100μl/s (cutoff). After the cannula is removed from the cannula passage215, the robot arm speeds and syringe flow rates are reset to theirinitial values. The cannula 21 is then cleaned at the appropriate washstations 101, 111 and flushes a sufficient volume of solvent to removeany and all memory of the previous reagent, on average 1000 μl per washstation.

[0120] Preparation of a slurry is initiated by adding a solid supportedcatalyst to each reaction vial 165. The solid supported catalyst isprepared as is well known in the art, as disclosed for example in U.S.Pat. No. 5,643,847 or U.S. Pat. No. 5,712,352, each of which isincorporated herein by reference. After the above described washsequence has concluded, the two robot arms 307L, 307R move at the samespeed to move the cannulas 21 to their respective orbital shakers 141.Each shaker supports a rack 17 comprising two rack panels each holding24 individual 1.0 ml mixing vials, spaced in an 8×3 array, 48 vialstotal. Of the 48 mixing vials 24 contain a solid supported catalyste.g., 10 mg of solid supported catalyst to be delivered to correspondingreactor vials 165. The shaker is operated at a speed of 1100 RPM. Thecannula 21 aspirates diluent from a separate reagent vial accessible tothe robot system 21, following which the cannula is moved to the firstmixing vial where it dispenses 500 μl of diluent, in this case toluene.The cannula 21 is then washed at a station 101, 111 for a sufficientperiod of time, during which the solid supported catalyst particles inthe mixing vial 165 are suspended in the diluent to provide asubstantially homogeneous slurry. After washing, the cannula moves backto a position just above the rim of the mixing vial 15 containing theslurry for the first reaction vial 165 and pauses. This pause allows therobot arm speed and the syringe flow rate to be decreased to the initialvalues noted above, except the Z-deceleration component is set to 250mm/sec² and the syringe flow is changed to 50 μl/sec (start), 25 μl/sec(stop) and 50 μl/sec (cutoff). As described, the lower speed allows thecannula to enter the slurry without altering the vortexing and allowsaspiration of substantially homogeneous slurry without selectivity.While the cannula is paused above the rim of the mixing vial, thesyringe pump is filled with 500 μl of a chaser solvent (toluene) fromthe same solvent reservoir. The cannula then descends into the slurryand pauses. 100 μl of slurry containing 1 mg of solid supported catalystis aspirated from the first mixing vial 15. The robot arm speed andsyringe flow rate are reset and the cannula 21 is moved to a vial on thesame rack 17 containing solvent and aspirates 50 μl of solvent to act asa liquid barrier. The cannula is then moved to the reactor modulecontaining the first reaction vial 165, and the injection sequencedescribed earlier and shown in FIGS. 12-14 is carried out. Prior tomovement of the cannula from the position shown in FIG. 13 to thedelivery position shown in FIG. 14, the speed of the robot arm isincreased to have a Z-acceleration component of 1450 mm/sec². Thisallows the cannula 21 to reach fluid delivery position as quickly aspossible. The syringe flow rate is also increased to 100 μl/sec (start),400 μl/sec (stop), 100 μl/sec (cutoff). Upon reaching the deliveryposition, the syringe pump 43 forces the entire contents of the cannula,i.e., solvent chaser, slurry, and liquid barrier, at the highestpossible flow rate. Once delivery is completed, the cannula is withdrawnfrom the cannula passage 215 in the manner previously described, thecannula moving first to the dwell position shown in FIG. 13, where therobot arm speed and syringe flow rate are decreased to their initialvalues, and then withdrawn completely from the cannula passage 215. Thecannula then goes through the appropriate wash routine. The sequence isrepeated for each and all reaction vials 165. Upon catalyst injection toeach reaction vial, polymerization occurs, allowing catalyst performancefrom a slurry to be evaluated In view of the above, it will be seen thatthe several objects of the invention are achieved and other advantageousresults attained.

[0121] As various changes could be made in the above constructionswithout departing from the scope of the invention, it is intended thatall matter contained in the above description or shown in theaccompanying drawings shall be interpreted as illustrative and not in alimiting sense.

1. Apparatus for parallel processing of multiple reaction mixtures, saidapparatus comprising a reactor having an exterior surface, vessels inthe reactor for holding said reaction mixtures, each vessel having acentral longitudinal axis, a cannula for introducing fluid reactionmaterial into the vessels, said cannula having a longitudinal axis, adistal end, and a port generally adjacent said distal end for deliveryof said reaction material from the cannula, cannula passages in thereactor extending between said exterior surface of the reactor and saidvessels, each cannula passage extending at an angle relative to saidcentral longitudinal axis of a respective vessel, and a robot systemoperable to insert the cannula through a selected cannula passage andinto a respective vessel for the delivery of said reaction material fromthe cannula to the respective vessel, and to withdraw the cannula fromthe selected cannula passage and respective vessel.
 2. Apparatus as setforth in claim 1 wherein said port of the cannula opens generallylaterally with respect to the longitudinal axis of the cannula wherebyreaction material is delivered from the cannula and directed into saidvessels in a downward direction generally parallel to said centrallongitudinal axis of each vessel.
 3. Apparatus as set forth in claim 1further comprising a sealing mechanism in each cannula passage forsealing against leakage of gas therepast when the cannula is insertedinto and withdrawn from the cannula passages.
 4. Apparatus as set forthin claim 3 wherein said sealing mechanism comprises a valve movablebetween a closed position for closing the cannula passage and an openposition permitting movement of the cannula through the passage, and aseal in the passage sealingly engageable with the cannula when the valveis in its open position.
 5. Apparatus as set forth in claim 3 whereinsaid seal is located on a side of the valve opposite the vessel. 6.Apparatus as set forth in claim 1 further comprising a wiper on thereactor adjacent an inlet end of each cannula passage for wiping theexterior surface of the cannula as it is inserted in the passage to wipeaway any material thereon.
 7. Apparatus as set forth in claim 1 whereinsaid robot system is operable to move said cannula to an angledorientation in which the cannula is held at an angle corresponding tothe angle the selected cannula passage extends relative to said centrallongitudinal axis of the respective vessel for insertion of the cannulainto the selected cannula passage.
 8. Apparatus as set forth in claim 7further comprising a sealing mechanism in each cannula passage forsealing against leakage of gas therepast when the cannula is insertedinto and withdrawn from the cannula passages, said sealing mechanismcomprising a valve movable between a closed position for closing thepassage and an open position permitting movement of the cannula throughthe passage, and a seal in the passage sealingly engageable with thecannula when the valve is in its open position, said seal being locatedon a side of the valve opposite said vessel.
 9. Apparatus as set forthin claim 8 wherein said robot system is operable to insert said cannulain said angled orientation into a cannula passage to a delivery positionin which the distal end of the cannula is downstream from the valve fordelivery of reaction material to a respective vessel, then to withdrawthe cannula to an intermediate position in which the distal end of thecannula is between the valve and said seal, the robot system holding thecannula in said intermediate position for a dwell period sufficient toallow the valve to close prior to completely withdrawing the cannulafrom the cannula passage.
 10. Apparatus as set forth in claim 7 whereinsaid robot system comprises an arm rotatable about a longitudinal axisextending generally parallel to the arm, a mount on the arm for mountingsaid cannula, and a rotating mechanism for rotating the arm about saidlongitudinal axis to move the cannula between said angled position and agenerally vertical position.
 11. Apparatus as set forth in claim 10wherein said rotating mechanism comprises an actuator for rotating saidarm in two directions, a first stop for limiting rotation of the arm inone direction to stop the arm at a position corresponding to said angledposition of the cannula, and a second stop for limiting rotation of thearm in an opposite direction to stop the arm at a position correspondingto said generally vertical position of the cannula.
 12. Apparatus as setforth in claim 11 wherein said actuator comprises a double-acting powercylinder.
 13. Apparatus as set forth in claim 10 wherein said cannulacomprises a long metal tube, and wherein said apparatus furthercomprises a cannula support on the mount engageable with the tubeintermediate the ends of the tube for supporting and stabilizing thetube in precise position as the cannula is moved.
 14. Apparatus as setforth in claim 13 wherein said cannula support comprises a body affixedto the cannula mount and a head mounted on the body and having anopening therein sized for a close clearance fit with said long metaltube, said head being movable relative to the body from an extendedposition in which the head is spaced from the body for engagement with amore distal portion of the tube, and a retracted position in which thehead is closer to the body for engagement with a more proximal portionof the tube to allow for insertion of the said more distal portion ofthe tube into a cannula passage.
 15. Apparatus as set forth in claim 1wherein said cannula comprises a reservoir for holding a volume of saidreaction material, said reservoir having an outside diameter, and a longthin tubular needle in fluid communication with said reservoir andhaving an outside diameter less than the outside diameter of thereservoir, said needle having a lateral opening constituting said portof the cannula.
 16. Apparatus as set forth in claim 1 further comprisinga heated wash tower having a well therein for receiving a portion of acannula to be cleaned, said tower having a heater for heating fluid inthe well to clean said portion of the cannula.
 17. A method of loadingfluid reaction material into a series of vessels in a reactor, eachvessel having a central longitudinal axis, said method comprising, insequence: (1) inserting a cannula through a cannula passage in saidreactor to a position in which the cannula extends at an angle relativeto the central longitudinal axis of a first vessel of said series ofvessels, and in which a distal end of the cannula is disposed in saidvessel, (2) delivering a fluid reaction material from said cannula intothe vessel, (3) withdrawing the cannula from said passage, and (4)repeating 1-3 for a second vessel.
 18. A method as set forth in claim 17wherein the cannula has a port adjacent its said distal end openinglaterally relative to a longitudinal axis of the cannula, said methodfurther comprising orienting said distal end of the cannula in thevessel so that said port faces downwardly for delivering reactionmaterial from the cannula in a downward direction.
 19. A method as setforth in claim 17 wherein said cannula has an outside surface, andwherein said method further comprises wiping the outside surface as thecannula is inserted in said cannula passage.
 20. A method as set forthin claim 17 wherein each cannula passage has a sealing mechanism thereinfor sealing against the leakage of gas therepast when the cannula isinserted into and withdrawn from the passages, said method comprisinginserting the cannula into said cannula passage to a point past saidsealing mechanism, and then delivering pressurized fluid reactionmaterial from the cannula into the vessel.
 21. A method as set forth inclaim 20 wherein said sealing mechanism comprises a valve movablebetween a closed position for closing the cannula passage and an openposition permitting movement of the cannula through the passage, and aseal in the passage sealingly engageable with the cannula when the valveis in its open position, said seal being located on a side of the valveopposite said vessel, said withdrawing step comprising withdrawing thecannula to an intermediate position in which the distal end of thecannula is located between the valve and said seal, and holding thecannula in said intermediate position for a dwell period sufficient toallow the valve to close before completely withdrawing the cannula fromthe cannula passage.
 22. A method as set forth in claim 17 wherein saidreaction material is a slurry comprising a catalyst fluid.
 23. A methodas set forth in claim 21 wherein said catalyst is disposed on aparticulate support.
 24. A method as set forth in claim 17 furthercomprising cleaning the cannula after withdrawing it from said cannulapassage, said cleaning comprising washing and rinsing the cannula usinga heated solution.
 25. A method as set forth in claim 17 furthercomprising cleaning the cannula after withdrawing it from said cannulapassage, said cleaning comprising subjecting said cannula to ultrasonicwaves.
 26. A cannula for use aspirating reactant materials anddelivering such materials to reaction vessels for the parallelprocessing of such materials, said cannula comprising a tubular metalreservoir having a longitudinal axis, an inside diameter defining ahollow interior for containing said reactant materials, an outsidediameter, a proximal end and a distal end, a long straight thin needleformed from metal tubing and coaxial with said reservoir, said needlehaving an outside diameter substantially less than the outside diameterof the reservoir and an inside diameter defining a flow passage throughthe needle, said needle further having a proximal end, a distal end, anda port adjacent said distal end for aspirating said reactant materialsinto the needle and delivering reactant materials from the needle, ametal transition joining the proximal end of the needle to the distalend of said reservoir so that the hollow of the interior of thereservoir is in fluid communication with the flow passage of the needle.27. A cannula as set forth in claim 26 wherein the reservoir, needle andtransition have interior surfaces which are seamed together to form acontinuous interior expanse of smooth metal extending from the reservoirto the transition to the needle.
 28. A cannula as set forth in claim 27wherein said transition is generally funnel-shaped to have an slopingside wall, a bottom wall, and a hole through the bottom wall receiving adistal end portion of the needle, the distal end of the needle beingflush with the interior surface of the transition.
 29. A cannula as setforth in claim 28 wherein said transition is joined to the reservoir andneedle by welds, and wherein the welds are polished to a smooth finishon the inside of the cannula.
 30. A cannula as set forth in claim 26wherein the port of the needle faces laterally away from saidlongitudinal axis.
 31. A cannula as set forth in claim 30 wherein theport of the needle is elongate in shape and has a minimum dimension ofabout 0.0155 in.
 32. Vessels for placement in a series of verticalcylindric wells in a parallel reactor, said reactor having cannulapassages extending at an angle off vertical from an exterior surface ofthe reactor to said wells, each cannula passage being adapted for thepassage therethrough of a cannula containing reaction material to bedelivered to a respective vessel, each vessel having a bottom and acylindric side wall extending up from the bottom and terminating in arim defining an open upper end of the vessel, said cylindric side wallhaving an inside diameter in the range of 0.5-2.5 in., said vesselhaving a volume in the range of 5-200 ml. and having an overall heightin the range of 1.0-4.0 in. whereby when the vessel is placed in saidwell, the open upper end of the vessel is disposed at an elevation belowsaid cannula passage where the cannula passage enters the well and ispositioned for entry of the cannula down through the open upper end ofthe vessel to a position below said rim for the delivery of reactantmaterials into the vessel.
 33. A method of preparing and delivering aslurry into a series of vessels in a reactor, said method comprising:(1) mixing a particulate solid material and a liquid dispersing mediumand agitating the mixture to form a substantially homogeneous firstslurry in which said particulate solid material is suspended in theliquid; (2) aspirating said first slurry into a cannula carried by arobot system while the slurry is substantially homogeneous, (3)operating the robot system to insert the cannula into the reactor; (4)delivering the slurry from the cannula into the vessel while the cannulais in said reactor, and (5) repeating steps 2-4 for a second vessel andoptionally a second slurry.
 34. A method as set forth in claim 33wherein said aspirating occurs during said agitating.
 35. A method asset forth in claim 33 wherein said slurry is delivered to said vesselwhile the slurry is still substantially homogenous.
 36. A method as setforth in claim 35 wherein said slurry is delivered to said vessel within60 seconds of said aspirating.
 37. A method as set forth in claim 33wherein said agitating is accomplished by vortexing.
 38. A method as setforth in claim 33 further comprising aspirating a barrier liquid intosaid cannula after aspirating said slurry and before delivering saidslurry.
 39. A method as set forth in claim 33 wherein said slurrycomprises a catalyst.
 40. A method as set forth in claim 39 wherein saidcatalyst is supported on said particulate solid material.
 41. A methodas set forth in claim 33 wherein said slurry is prepared less than 90minutes before delivery to said first vessel.
 42. A method as set forthin claim 33 wherein said vessel into which said slurry is delivered ispressurized.
 43. A method as set forth in claim 33 wherein said firstand second slurries are of different composition.